U.S. patent application number 13/081590 was filed with the patent office on 2012-10-11 for additives to mitigate catalyst layer degradation in fuel cells.
This patent application is currently assigned to Ford Motor Company. Invention is credited to Sumit Kundu, Jing Li, Scott McDermid, Keping Wang, Yunsong Yang.
Application Number | 20120258382 13/081590 |
Document ID | / |
Family ID | 46026755 |
Filed Date | 2012-10-11 |
United States Patent
Application |
20120258382 |
Kind Code |
A1 |
Li; Jing ; et al. |
October 11, 2012 |
ADDITIVES TO MITIGATE CATALYST LAYER DEGRADATION IN FUEL CELLS
Abstract
Ligand additives having two or more coordination sites in close
proximity can be used in the polymer electrolyte of membrane
electrode assemblies in solid polymer electrolyte fuel cells in
order to reduce the dissolution of catalyst, particularly from the
cathode, and hence reduce fuel cell degradation over time.
Inventors: |
Li; Jing; (Surrey, CA)
; Wang; Keping; (Richmond, CA) ; Yang;
Yunsong; (Surrey, CA) ; McDermid; Scott;
(Vancouver, CA) ; Kundu; Sumit; (Burnaby,
CA) |
Assignee: |
Ford Motor Company
Dearborn
MI
Daimler AG
Stuttgart
|
Family ID: |
46026755 |
Appl. No.: |
13/081590 |
Filed: |
April 7, 2011 |
Current U.S.
Class: |
429/492 ;
429/535; 521/27 |
Current CPC
Class: |
C08J 5/2237 20130101;
H01M 2004/8689 20130101; H01M 4/92 20130101; C08J 5/2206 20130101;
H01M 8/1051 20130101; H01M 8/1004 20130101; H01M 8/1018 20130101;
Y02E 60/50 20130101 |
Class at
Publication: |
429/492 ;
429/535; 521/27 |
International
Class: |
H01M 8/10 20060101
H01M008/10; C08J 5/22 20060101 C08J005/22; H01M 8/00 20060101
H01M008/00 |
Claims
1. A proton conducting composite polymer electrolyte for a membrane
electrode assembly in a solid polymer electrolyte fuel cell
comprising a proton conducting ionomer and an amount of a ligand
additive wherein the ligand comprises a molecule or polymer thereof
wherein the chemical structure of the molecule is selected from the
group consisting of: ##STR00005## ##STR00006## wherein R and R' are
selected from the group consisting of H, OH, NH.sub.2,
CH.sub.3(CH.sub.2).sub.n, and an aromatic group, and wherein n is
an integer from 0 to 10.
2. The composite polymer electrolyte of claim 1, wherein R is the
same as R'.
3. The composite polymer electrolyte of claim 1, wherein the ligand
is 5,8-dihydroxy-1,4-naphthoquinone, 2,3-pyridinedicarboxylic acid,
3,4-pyridinedicarboxylic acid, or 2,6-pyridine dicarboxylic
acid.
4. The composite polymer electrolyte of claim 3, wherein the ligand
is 5,8-dihydroxy-1,4-naphthoquinone, or 2,6-pyridine dicarboxylic
acid.
5. The composite polymer electrolyte of claim 1, wherein the amount
of the ligand additive in the composite polymer electrolyte is
greater than or about 2% by weight of the proton conducting
ionomer.
6. The composite polymer electrolyte of claim 5, wherein the amount
of the ligand additive in the composite polymer electrolyte is from
about 2% to about 5% by weight of the proton conducting
ionomer.
7. The composite polymer electrolyte of claim 1, wherein the ligand
is part of a complex comprising a metal and the ligand.
8. The composite polymer electrolyte of claim 1, wherein the proton
conducting ionomer is perfluorosulfonic acid ionomer or hydrocarbon
ionomer.
9. A membrane electrode assembly for a solid polymer electrolyte
fuel cell comprising an anode catalyst layer, a membrane
electrolyte, a cathode catalyst layer and the composite polymer
electrolyte of claim 1.
10. The membrane electrode assembly of claim 9, wherein the cathode
catalyst layer comprises the composite polymer electrolyte of claim
1.
11. A solid polymer electrolyte fuel cell comprising the membrane
electrode assembly of claim 9.
12. A method of making the composite polymer electrolyte of claim
1, comprising: preparing an amount of the ligand in a solution or
dispersion; and mixing the solution or dispersion comprising the
ligand with a solution or dispersion comprising the proton
conducting ionomer, thereby preparing the composite polymer
electrolyte in the solution or dispersion.
13. A method of making the composite polymer electrolyte of claim
1, comprising: mixing an amount of the ligand in a solution or
dispersion comprising the proton conducting ionomer, thereby
preparing the composite polymer electrolyte in the solution or
dispersion.
14. A method of preventing dissolution of a cathode catalyst in a
solid polymer electrolyte fuel cell comprising a membrane electrode
assembly comprising an anode catalyst layer, a membrane
electrolyte, and a cathode catalyst layer, the method comprising
using the composite polymer electrolyte of claim 1 in the cathode
catalyst layer.
Description
BACKGROUND
[0001] 1. Field of the Invention
[0002] This invention relates to additives for the proton
conducting polymer electrolyte used in catalyst layers in fuel
cells. In particular, it relates to additives for reducing catalyst
dissolution, especially from the cathode.
[0003] 2. Description of the Related Art
[0004] Proton exchange membrane fuel cells (PEMFCs) convert
reactants, namely fuel (such as hydrogen) and oxidant (such as
oxygen or air), to generate electric power. PEMFCs generally employ
a proton conducting polymer membrane electrolyte between two
electrodes, namely a cathode and an anode. A structure comprising a
proton conducting polymer membrane sandwiched between two
electrodes is known as a membrane electrode assembly (MEA). MEA
durability is one of the most important issues for the development
of fuel cell systems in either stationary or transportation
applications. For automotive applications, an MEA is required to
demonstrate durability of about 6,000 hours.
[0005] Degradation of the catalyst during operation of the fuel
cell, especially during start up or shut down in which the
transient potential at the cathode could be over 1 V, is a critical
issue to address in order to maintain cell performance without
significant decay for over 5,000-6,000 hours of operation. Cathode
catalyst layer degradation and the associated decay in fuel cell
performance may be caused by 1) loss of Pt catalyst surface area
due to formation of larger particles from smaller particle Pt
dissolution (Ostwald Ripening) or coalescence of Pt nanoparticles
by thermal motion (sintering) or loss of the carbon support
typically employed due to carbon corrosion; 2) Pt dissolution and
migration into the catalyst electrolyte, membranes, or washed out
altogether in by-product water; 3) contamination of ionomer
electrolyte by dissolved metal ions from catalyst; and 4)
contamination of the catalyst surface by chemicals resulting from
ionomer degradation.
[0006] One of ways to mitigation the cathode catalyst degradation
is to decrease the dissolution of Pt catalyst during fuel cell
operation. Pt.sup.z+ ions most probably do not exist as free
species in the ionomer phase or in solution. They have to be
associated with counter ions in order to maintain charge
neutrality. Fluorine (F.sup.-), chlorine (Cl.sup.-) and other
halogen ions are common counter ions that can form complexes with
Pt.sup.z+ ions to make them water soluble. Halide anions are strong
ligands and they may promote ligand exchange with O.sup.2- and
de-passivate a Pt oxide layer, thereby accelerating the dissolution
of the Pt. Halide anions can come from residual Pt chloride that is
commonly used in the production of Pt nanoparticles. F.sup.- can be
released from the perfluorosulfonic acid (PFSA) polymer membrane or
ionomer due to the ionomer degradation in the catalyst layer during
fuel cell operation. A decrease of halide anions in the catalyst
layer could lower the Pt dissolution, thereby mitigating cathode
catalyst layer degradation. P. Trogadas and V. Ramani added a
peroxide decomposition catalyst (MnO.sub.2) into the anode and
cathode electrocatalysts to facilitate both electrochemical oxygen
reduction and hydrogen peroxide decomposition to water and oxygen
[P. Trogadas, V. Ramani, Journal of Power Sources 174 (2007)
159-163]. By lowering hydrogen peroxide concentration within the
electrode, the fluorine release rate associated with the
decomposition was decreased. However, the drawback was a loss of
catalyst activity by adding the MnO.sub.2 in the catalyst
layer.
[0007] In published patent application WO 2008/032802 A1, it was
claimed that a complex of Pt having ligands such as acetylacetone
and ethylene di-amine tetra-acetic acid (EDTA) as coordinating
atoms could mitigate Pt dissolution from catalyst surface due to
equilibrium shifting toward solid Pt. In the disclosed voltage
cycling test (from 0.05-1.2 V in nitrogen and hydrogen), 10% of
acetylacetone in the cathode catalyst layer showed the lowest
voltage decay. However, such highly water soluble ligands
(acetylacetone solubility: 160 g in one liter of water) are not
expected to stay in the catalyst layer long during operation. They
will be washed out soon after the load is applied to the fuel cell.
Fluorine ions and fluoride fragments, for example,
pentafluoropropionic acid (PFPA, CF.sub.3CF.sub.2COOH), may form
during fuel cell operation as a result of membrane degradation.
Fluorine ions formed in the membrane may diffuse into the catalyst
layer and accelerate Pt dissolution. Fluoride fragments may
contaminate the Pt surface and lower its activity. Therefore,
decreasing the fluorine release rate associated with degradation of
the membrane by increasing its chemical stability could mitigate
catalyst layer degradation.
[0008] Different additives to the membrane electrolyte have been
studied for purposes of decreasing the fluorine release rate. These
additives include: 1) metal elements or compositions containing
metal elements or metal alloys that act as a free radical scavenger
or a hydrogen peroxide decomposition catalyst (e.g. US2004043283);
2) phenol or phenol derivatives that can be a small molecule or a
polymer (e.g. US2006046120); 3) organic crown compounds (e.g.
US20060222921) or macrocyclic compounds containing metal or
metalloids (e.g. WO2007144633); and 4) cation chelating agents to
reduce formation of free radicals (e.g. U.S. Pat. No.
6,607,856).
[0009] Additives are also disclosed in WO2005060039 to address the
problem in PEM fuel cell durability of premature failure of the
ion-exchange membrane. The degradation of the ion-exchange membrane
by reactive hydrogen peroxide species can be reduced or eliminated
by the presence of an additive in the anode, cathode or
ion-exchange membrane. The additive may be a radical scavenger, a
membrane cross-linker, a hydrogen peroxide decomposition catalyst
and/or a hydrogen peroxide stabilizer. The presence of the additive
in the membrane electrode assembly (MEA) may however result in
reduced performance of the PEM fuel cell. In particular, suggested
additives include an organometallic Mn (II) or Mn (III) complex
having an organic ligand selected from CyDTA, ENTMP, gluconate,
N,N'-bis(salicylidene)propylenediamine, porphoryns,
phthalocyanines, phenanthroline, hydrazine,
pyrocatechol-3,5-disulphonic acid disodium salt,
triethylenetetraamine, shiff base macrocycles and EDDA.
[0010] In commonly owned U.S. patent application Ser. No.
12/615,671, with the title "Composite Proton Conducting Membrane
with Low Degradation and Membrane Electrode Assembly for Fuel
Cells" and filed on Nov. 10, 2009, certain ligand additives (e.g.
1,10-phenanthroline or 2,2'-bipyridine) were disclosed that meet
many of these needs. The use of these ligand additives in the
membrane and/or catalyst layers can improve durability but,
depending on testing conditions, there may be a modest penalty in
fuel cell performance (e.g. 3 times better stability might be
obtained but with a 20 mV loss in voltage under load). Preferably,
both durability and performance of fuel cells would be improved
with appropriate additives.
[0011] In PCT patent application PCT/EP2010/006836, also commonly
owned by the present applicant, certain additives were disclosed
for polymer electrolytes in order to improve both durability and
performance. The additives were chemical complexes comprising
certain metal and organic ligand components.
[0012] There remains a continuing need for improved additives to
reduce MEA degradation and, in particular, to prevent dissolution
of electrode catalysts during operation. This invention fulfills
these needs and provides further related advantages.
SUMMARY
[0013] It has been discovered that incorporating certain strongly
coordinating ligand additives in the proton conducting ionomer
electrolyte of a solid polymer electrolyte fuel cell can be
beneficial for fuel cell performance, and particularly to reduce
catalyst dissolution and the various problems associated with this.
The ligand additives in this composite polymer electrolyte are
characterized by an aromatic or heterocyclic structure having two
or more coordination sites in close proximity and thus comprise a
molecule or polymer thereof wherein the chemical structure of the
molecule is selected from the group consisting of:
##STR00001## ##STR00002##
[0014] in which R and R' are selected from the group consisting of
H, OH, NH.sub.2, CH.sub.3(CH.sub.2).sub.n, and an aromatic group,
and in which n is an integer from 0 to 10. R and R' may be
different or the same moiety. In particular, the ligand can be
5,8-dihydroxy-1,4-naphthoquinone, 2,3-pyridinedicarboxylic acid,
3,4-pyridinedicarboxylic acid, or 2,6-pyridine dicarboxylic
acid.
[0015] In particular, the amount of additive incorporated can be
greater than or about 2% by weight with respect to that of the
proton conducting ionomer. As demonstrated in the Examples to
follow, amounts up to 5% by weight can be incorporated and be
effective. The proton conducting ionomer in the composite can be
perfluorosulfonic acid ionomer or hydrocarbon ionomer.
[0016] The composite polymer electrolyte of the invention may be
used anywhere that electrolyte is normally employed in a fuel cell.
However, it is particularly useful in preventing dissolution of a
cathode catalyst in a solid polymer electrolyte fuel cell. In this
regard, the composite polymer electrolyte is desirably employed in
the cathode catalyst layer of the fuel cell.
[0017] It can be further advantageous to combine the benefits
obtained when using additives of the instant invention with the
benefits obtained when using additives from the aforementioned PCT
patent application PCT/EP2010/006836. For instance, the former
additives may for employed in the cathode catalyst of a fuel cell
in combination with employing the latter additives in the membrane
electrolyte.
[0018] One method for preparing such a composite polymer
electrolyte is to prepare an amount of ligand in a solution or
dispersion and then to mix it with another solution or dispersion
comprising the desired proton conducting ionomer thereby preparing
the composite polymer electrolyte in the resulting solution or
dispersion. Alternatively, the ligand may instead be added directly
to a solution or dispersion comprising the desired proton
conducting ionomer.
[0019] The composite polymer electrolyte solution or dispersion can
then be mixed with a suitable catalyst, catalyst support, and/or
other materials and solvents to make a catalyst ink or
alternatively the other catalyst ink materials may be added to the
aforementioned solutions/dispersions to make a catalyst ink.
Alternatively, the ligand additive, the proton conductive ionomer,
and suitable solvents, catalyst and catalyst support can be mixed
together directly to make a catalyst ink.
[0020] These and other aspects of the invention are evident upon
reference to the attached Figures and following detailed
description.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] FIG. 1 compares the voltage versus current density
(polarization) curves of the Inventive Example 1 and the
Comparative Example cells, both before and after cycle testing.
[0022] FIGS. 2a and 2b show TEM images of representative membrane
electrolyte cross-sections taken after cycle testing from the
Comparative Example and the Inventive Example 1 cells
respectively.
DETAILED DESCRIPTION
[0023] In the present invention, certain oxygen containing ligand
additives are used in the polymer electrolyte of membrane electrode
assemblies in solid polymer electrolyte fuel cells. The ligand
additives exhibit low solubility in water and thus essentially do
not wash out from the fuel cell with time and their presence can
reduce the dissolution of electrode catalyst, particularly of the
cathode catalyst, and thus can reduce fuel cell degradation over
time. Several such ligand additives have been demonstrated
effective in the Examples to follow.
[0024] The ligand additives coordinate strongly with other species
and are characterized by an aromatic or heterocyclic structure
having two or more coordination sites in close proximity. They
comprise a molecule or a polymer of a molecule selected from the
group consisting of:
##STR00003## ##STR00004##
[0025] in which R and R' are selected from the group consisting of
H, OH, NH.sub.2, CH.sub.3(CH.sub.2).sub.n, and an aromatic group,
and in which n is an integer from 0 to 10. In the preceding, R and
R' may be different or the same moiety. In particular, the ligand
can be 5,8-dihydroxy-1,4-naphthoquinone, 2,3-pyridinedicarboxylic
acid, 3,4-pyridinedicarboxylic acid, or 2,6-pyridine dicarboxylic
acid.
[0026] With regard to employing polymer ligand additives, the
complex forming units can be either on the polymer backbone or on
side chains. The additives can be homopolymers of complex forming
units or copolymers of complex forming units. Copolymers can be
random or block copolymers. When a complex forming unit is on the
polymer side chain, it can be directly attached to the polymer
backbone or attached via a spacer. The polymer backbone can be an
aromatic, semi- or perfluoro aliphatic polymer. On each side chain,
there can be one complex forming unit or multiple complex forming
units.
[0027] In addition, the presently disclosed ligand additives are
selected based on an anticipated ability to chelate with ions
arising from dissolution of the catalyst. As discussed later, after
forming complexes in the catalyst layer, such ions may no longer
exchange with protons in acid groups in the ionomer
electrolyte.
[0028] The above-mentioned additives are employed in the cathode
catalyst layer in order to improve the lifetime of fuel cells.
[0029] Such composite polymer electrolytes can be prepared simply
by first preparing an amount of the ligand additive in solution or
dispersion, then mixing the ligand solution or dispersion with
another solution or dispersion comprising the desired proton
conducting ionomer. Alternatively, the ligand may be added directly
to a solution or dispersion comprising the desired proton
conducting ionomer. The ionomer employed can be conventional
perfluorosulfonic acid ionomer or hydrocarbon ionomer and the
solution or dispersion can include suitable amounts of other
additives and solvents. More typically however, the composite
dispersion/solution can be used directly to prepare appropriate
fuel cell components. For instance, the dispersion/solution may be
used directly to cast membrane electrolyte, to prepare catalyst
layers, or otherwise be incorporated into membrane electrode
assemblies in any conventional manner as desired. For example, in
one preferred embodiment, the dispersion/solution can be spray
coated onto the surface of a gas diffusion electrode (GDE). The
coated GDE can then be bonded with a proton conducting membrane to
make a membrane electrode assembly. In another preferred
embodiment, a catalyst or conventional catalyst ink can be mixed
with the composite dispersion/solution to make a catalyst ink, and
then the ink can be coated onto a membrane to make a catalyst
coated membrane or onto a gas diffusion layer to make GDE.
[0030] Any effective amount of additive may be considered in the
composite electrolyte. Amounts like those in the Examples, e.g. in
the range from about 2% to 5% by weight to that of the ionomer in
the catalyst ink may be used. Preferably, a minimal amount of
additive is used to obtain the desired results. Thus, as
illustrated in the Examples following, amounts of 5% and under by
weight can be effective when used in a catalyst layer.
[0031] Without being bound by theory, it is believed that the
presently disclosed ligand additives mitigate the voltage decay of
a fuel cell that results from catalyst dissolution and
contamination associated with degradation of the ionomer
electrolyte. These ligand additives can provide several useful
functions. They are capable of chelating with metal ions,
especially the Fenton ions like iron, nickel, cobalt, copper, etc.
and inactivating them as a result and thereby preventing ionomer
decomposition with associated release of fluoride decomposition
product. Importantly however, the additives can particularly form
complexes with Pt and other transition metals in the catalysts
typically used in such fuel cells. By complexing with any ions
present as a result of catalyst dissolution, the ligand additives
can prevent the ions from linking to acid groups in the ionomer
electrolyte, thereby contaminating the ionomer. Such dissolved ions
could otherwise contaminate the ionomer in the catalyst layer
and/or membrane electrolyte through ion exchange with protons
therein and thereby lower the ionic conductivity of the ionomer. In
turn, this would increase ohmic and mass transfer losses of the
MEA, especially under high current density and dry operation
conditions.
[0032] The following examples are illustrative of the invention but
should not be construed as limiting in any way.
EXAMPLES
[0033] Polymer electrolyte samples comprising ligand additives of
the invention and membrane electrode assemblies (MEAs) using these
samples in the cathode catalyst layers were prepared as described
below. In addition, MEAs were prepared either with other additives
in the catalyst layer or with no additives for illustrative and
comparative purposes. Test fuel cells were made with each MEA and
were operated with the results being summarized below.
Inventive Example 1
[0034] A membrane electrolyte was prepared from a dispersion
comprising a mixture of 1,10-phenanthroline-5-amino additive,
MnO.sub.2, and a commercially available PFSA ionomer dispersion
having a solids concentration of 22%. (This composition was
selected to obtain improved performance in accordance with the
teachings of the aforementioned PCT application PCT/EP2010/006836.
The amount of 1,10-phenanthroline-5-amino additive was 0.5 weight %
to that of the PFSA. The molar ratio of 1,10-phenanthroline-5-amino
additive to Mn was 4:1). The mixture was stirred overnight at
50.degree. C. and a membrane electrolyte sample was cast from
solution thereafter.
[0035] Then, a mixture comprising commercially obtained
naphthazarin (5,8-dihydroxy-1,4-naphthoquinone) and Nafion.RTM.
ionomer (EW 950) dispersion was prepared in which the amount of
naphthazarin to ionomer was 2% by weight. The mixture was stirred
for about 2 to 4 hours at room temperature. Commercially obtained
carbon supported catalyst was then mixed into the dispersion in a
solid weight ratio of 33/67 (ionomer/supported catalyst). The
resulting ink was then coated onto a PTFE release sheet and the
dried coating was then transferred to the aforementioned membrane
electrolyte sample to make a "half-CCM" or half-catalyst coated
membrane in which the catalyst layer was the cathode catalyst. The
Pt loading here was 0.27 mg/cm.sup.2.
[0036] A conventional anode with a Pt loading of 0.3 mg/cm.sup.2
was then bonded to this half-CCM at 150-160.degree. C. under
pressure for 2.5 minutes, thereby completing the sample MEA.
Inventive Example 2
[0037] A MEA similar to that of Inventive Example 1 was prepared
except that instead of naphthazarin, 2,6-pyridine dicarboxylic acid
was used as the oxygen containing ligand additive in the cathode
catalyst layer instead. The amount of 2,6-pyridine dicarboxylic
acid to ionomer was 5% by weight.
Illustrative Example
[0038] A MEA similar to that of Inventive Example 1 was prepared
except that instead of naphthazarin, 1,10-phenanthroline-5-amino
additive was used in the cathode catalyst layer instead (this
additive being a ligand which is the same as that appearing in the
membrane electrolyte). The amount of 1,10-phenanthroline-5-amino
additive to ionomer was 1% by weight.
Comparative Example
[0039] For comparative purposes, a MEA similar to that of Inventive
Example 1 was prepared except that there was no naphthazarin or
other additive in the cathode catalyst layer nor in the
membrane.
[0040] Fuel cells with 48 cm.sup.2 active area were then assembled
using each of the above MEA samples. 5 different samples were
tested at the same time using a 5 cells stack. The stack was
subjected to an accelerated stress test which focused primarily on
cathode catalyst layer degradation. This involved subjecting each
cell in the 5 cell stack to voltage cycling between 0.6 and 1 volts
using a square wave cycle of 2 sec and 10 sec duration
respectively. Air and hydrogen were used as reactant gases at gas
stoichiometries of 12 and 9 respectively, with both supplied to the
stack at 100% relative humidity. The operating temperature of the
stack was 80.degree. C. Cell performance was evaluated by obtaining
polarization curves (voltage versus current density) prior to
cycling and then again after 20,000 cycles. Thereafter, the stack
and cells were disassembled. Representative cross-sections were
obtained from various locations within the cells and these were
observed under a scanning electron microscope (SEM). Certain
samples were also observed under a transmission electron microscope
(TEM).
[0041] FIG. 1 shows the voltage versus current density
(polarization) curves obtained for the cells comprising the
Inventive Example 1 and the Comparative Example MEAs, both before
and after cycle testing. The initial polarization curves for both
cells were about the same (with the Inventive Example 1 cell
showing slightly better performance). After cycle testing however,
the Comparative Example cell showed a voltage drop of approximately
50 mV from its initial value at 1.7 A/cm.sup.2. The Inventive
Example 1 cell on the other hand showed only a 10 mV voltage drop
at this current density. After disassembly and cross-section, a
significant dense band of Pt was clearly seen in the membrane
electrolyte from the Comparative Example cell in the SEM images. No
visible Pt was evident in the electrolyte of Inventive Example 1
cell. FIGS. 2a and 2b show TEM images for representative membrane
cross-sections cross-sections from the Comparative Example cell and
the Inventive Example 1 cell respectively. The scale in each Figure
is the same and is indicated by the 100 nm bar at the bottom of
each Figure. A substantial amount of Pt was evident in FIG. 2a (the
dark squares) while only a tiny amount of Pt was apparent in FIG.
2b (the small dark dot).
[0042] In a like manner, the initial polarization curve for the
Inventive Example 2 cell was about the same as that of the
Comparative Example cell. After cycle testing, the Inventive
Example 2 cell showed a 20 mV voltage drop from its initial value
at 1.7 A/cm.sup.2, which was substantially better than the 50 mV
drop seen in the Comparative Example cell. Under the SEM, no Pt
band was observed in the vicinity of the reactant inlets or in the
middle of the cell. However, a Pt band was evident near the
reactant outlets.
[0043] The initial polarization curve for the Illustrative Example
cell was again slightly better than that of the Comparative Example
cell. After cycle testing, the Illustrative Example cell showed a
20 mV voltage drop from its initial value at 1.7 A/cm.sup.2, which
was substantially better than the 50 mV drop seen in the
Comparative Example cell. Under the SEM, no Pt band was evident
anywhere in the membrane from the Illustrative Example cell.
[0044] Thus, all the above Inventive and Illustrative cells show
improved results with regards to cycle life testing and dissolution
of the cathode catalyst. The results can be comparable or better
than those obtained when employing additives like those in the
aforementioned PCT application PCT/EP2010/006836.
[0045] All of the above U.S. patents, U.S. patent application
publications, U.S. patent applications, foreign patents, foreign
patent applications and non-patent publications referred to in this
specification, are incorporated herein by reference in their
entirety.
[0046] While particular elements, embodiments and applications of
the present invention have been shown and described, it will be
understood, of course, that the invention is not limited thereto
since modifications may be made by those skilled in the art without
departing from the spirit and scope of the present disclosure,
particularly in light of the foregoing teachings. Such
modifications are to be considered within the purview and scope of
the claims appended hereto.
* * * * *